DE2858248C2 - - Google Patents
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- DE2858248C2 DE2858248C2 DE2858248A DE2858248A DE2858248C2 DE 2858248 C2 DE2858248 C2 DE 2858248C2 DE 2858248 A DE2858248 A DE 2858248A DE 2858248 A DE2858248 A DE 2858248A DE 2858248 C2 DE2858248 C2 DE 2858248C2
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- chlorine
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- fluorine
- bromine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/2635—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving a phosphorus compound, e.g. Wittig synthesis
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/40—Halogenated unsaturated alcohols
- C07C33/42—Halogenated unsaturated alcohols acyclic
- C07C33/423—Halogenated unsaturated alcohols acyclic containing only double bonds as unsaturation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/40—Unsaturated compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5428—Acyclic unsaturated phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
Description
Das deutsche Patent 28 02 962 betrifft Cyclopropancarbonsäureesterderivate der allgemeinen FormelGerman patent 28 02 962 relates to cyclopropane carboxylic acid ester derivatives the general formula
in der einer der Substituenten R¹ und R² für eine Gruppe der Formelin which one of the substituents R¹ and R² for a group of the formula
W(CF₂) W (CF₂)
wobei W Wasserstoff, Fluor oder Chlor ist und m den Wert 1 oder 2 hat, steht und der andere für Fluor, Chlor oder Brom oder eine Gruppe der Formelwhere W is hydrogen, fluorine or chlorine and m is 1 or 2, and the other is fluorine, chlorine or bromine or a group of the formula
wobei X, Y und Z unabhängig voneinander Wasserstoff, Fluor oder Chlor sind, steht und R³ Wasserstoff oder eine Cyan- oder Äthinylgruppe bedeutet.where X, Y and Z are independently hydrogen, Are fluorine or chlorine, and R³ is hydrogen or one Cyan or ethynyl group means.
Diese Verbindungen besitzen sehr gute insektizide Eigenschaften und eine gute Beständigkeit gegenüber Abbau durch Licht. Durch letztere Eigenschaft unterscheiden sie sich von ähnlichen natürlich vorkommenden Cyclopropancarbonsäurederivaten, von denen seit langem bekannt ist, daß sie insektizide Eigenschaften besitzen. These compounds have very good insecticidal properties and good resistance to degradation through light. They distinguish by the latter property from similar naturally occurring cyclopropanecarboxylic acid derivatives, of which have long been known that they have insecticidal properties.
Die im vorstehenden Anspruch 1 definierten Verbindungen der allgemeinen Formel (IV) eignen sich als Zwischenprodukte zur Herstellung der Verbindungen der obigen allgemeinen Formel (I). So können beispielsweise die in der genannten Patentschrift beschriebenen Verbindungen dadurch hergestellt werden, daß ein Niederalkylester der allgemeinen FormelThe compounds defined in claim 1 above the general formula (IV) are suitable as intermediates for the preparation of the compounds of the above general Formula (I). For example, those in the compounds described above be produced that a lower alkyl ester of general formula
worin R⁴ für Niederalkyl mit bis zu 6 Kohlenstoffatomen, vorzugsweise Methyl oder Äthyl, steht und R¹ und R² die oben angegebenen Bedeutungen besitzen, mit einem Alkohol der allgemeinen Formelwherein R⁴ is lower alkyl with up to 6 carbon atoms, preferably methyl or ethyl, and R¹ and R² are the have the meanings given above, with an alcohol the general formula
zur Bewirkung einer Umesterungsreaktion erhitzt wird.is heated to effect a transesterification reaction.
Bevorzugte erfindungsgemäße Zwischenprodukte sind in den vorstehenden Patentansprüchen 2 bis 10 näher beschrieben.Preferred intermediates according to the invention are in the above claims 2 to 10 described in more detail.
Die erfindungsgemäßen Verbindungen können wie die Verbindungen der allgemeinen Formel (I) in verschiedenen geometrischen und stereoisomeren Formen existieren. So gibt es cis- und trans-Isomere, die sich aus dem Substitutionsschema des Cyclopropanrings ergeben, und E- und Z-Isomere, die sich aus der substituierten Vinylgruppe ergeben, wenn R¹ nicht das gleiche wie R² ist. Zusätzlich können zwei der drei Kohlenstoffatome des Cyclopropans in entweder der R- oder der S-Konfiguration existieren, da sie asymmetrisch substituiert sind.The compounds according to the invention can, like the compounds of the general formula (I) in various Geometric and stereoisomeric forms exist. So there are cis and trans isomers that result from the substitution scheme of the cyclopropane ring, and E- and Z isomers derived from the substituted vinyl group if R¹ is not the same as R². In addition can be two of the three carbon atoms of cyclopropane exist in either the R or S configuration, because they are asymmetrically substituted.
Die Verbindungen der allgemeinen Formel (IV), worin Q für Hydroxy steht, können durch Hydrolyse der Verbindungen der allgemeinen Formel (IV), worin Q für Niederalkoxy steht, erhalten und durch Umsetzung mit beispielsweise Thionylchlorid oder Thionylbromid in Verbindungen der allgemeinen Formel (IV), worin Q für Chlor oder Brom steht, umgewandelt werden. Alle Verbindungen der allgemeinen Formel (IV) können entweder direkt oder indirekt zur Herstellung der insektizid aktiven Ester der allgemeinen Formel (I) gemäß obiger Vorschrift verwendet werden.The compounds of the general formula (IV), in which Q is Hydroxy can be obtained by hydrolysis of the compounds of the general formula (IV), wherein Q is lower alkoxy stands, received and by implementation with, for example Thionyl chloride or thionyl bromide in compounds of the general Formula (IV) in which Q represents chlorine or bromine, being transformed. All connections of the general Formula (IV) can be prepared either directly or indirectly the insecticidally active esters of the general Formula (I) can be used according to the above regulation.
Die Verbindungen der allgemeinen Formel (IV), worin Q für Niederalkoxy mit bis zu 6 Kohlenstoffatomen steht, das sind also die Verbindungen der obigen allgemeinen Formel (II), können z. B. durch die in den vorstehenden Ansprüchen 11 bis 19 angegebenen Verfahren erhalten werden.The compounds of the general formula (IV), in which Q is Lower alkoxy with up to 6 carbon atoms, that are the compounds of the general formula above (II), e.g. B. by the in the preceding claims 11 to 19 specified processes can be obtained.
Beispiele für Metallkatalysatoren bei dem Verfahren der vorstehenden Ansprüche 11 bis 14 sind pulverisiertes Kupfer oder pulverisierte Kupferbronze.Examples of metal catalysts in the process of preceding claims 11 to 14 are powdered Copper or powdered copper bronze.
Die Ausgangsverbindung der allgemeinen Formel (V) des vorstehenden Patentanspruchs 11 kann dadurch erhalten werden, daß man eine Verbindung der allgemeinen Formel (VI) des vorstehenden Anspruchs 15 einer Dehydratisierung mit beispielsweise Phosphorpentoxid unterwirft.The starting compound of the general formula (V) of above claim 11 can be obtained be that a compound of the general formula (VI) of claim 15 above for dehydration with, for example, phosphorus pentoxide.
Das Verfahren der vorstehenden Ansprüche 15 und 16 ist nicht auf die Herstellung von Verbindungen anwendbar, worin eines der Symbole R¹ und R² für Halogen steht, ist aber sehr nützlich für die Herstellung von Verbindungen, worin R¹ und R² beide Trifluoromethyl sind oder worin eines der Symbole R¹ und R² Trifluoromethyl und das andere Difluoromethyl ist.The method of claims 15 and 16 above not applicable to the preparation of compounds in which one of the symbols R¹ and R² represents halogen but very useful for making connections, wherein R¹ and R² are both trifluoromethyl or wherein one of the symbols R¹ and R² trifluoromethyl and the other Is difluoromethyl.
Die Verbindungen der allgemeinen Formel (VI) des vorstehenden Anspruchs 15 können dadurch erhalten werden, daß man ein Keton der allgemeinen FormelThe compounds of the general formula (VI) of the above Claim 15 can be obtained that you have a ketone of the general formula
mit 3-Methylbut-1-en, vorzugsweise unter Druck, umsetzt.with 3-methylbut-1-ene, preferably under pressure.
Geeignete Basen für die Durchführung der Verfahren der vorstehenden Ansprüche 17 und 18 sind tertiäre Amine, wie Pyridin, Triäthylamin, Diäthylanilin und N-Methylpiperidin, und auch Alkalimetall-niederalkoxide, das sind solche mit bis zu 6 Kohlenstoffatomen, wie z. B. Natriummethoxid, Natriumäthoxid und Natrium- und Kalium-t-butoxid. Dieses Verfahren wird zweckmäßig in einem Verdünnungs- oder Lösungsmittel für den Reaktionsteilnehmer und die Base ausgeführt.Suitable bases for performing the procedures of preceding claims 17 and 18 are tertiary amines, such as pyridine, triethylamine, diethylaniline and N-methylpiperidine, and also alkali metal lower alkoxides that are those with up to 6 carbon atoms, such as. B. sodium methoxide, Sodium ethoxide and sodium and potassium t-butoxide. This process is conveniently carried out in a dilution or solvent for the reactant and the Base executed.
Mindestens 2 Mol Base sind erforderlich, um die Verbindungen der allgemeinen Formel (VIII) in die Verbindungen der allgemeinen Formel (IV), worin R für Alkoxy mit 1 bis 6 Kohlenstoffatomen steht, umzuwandeln. Diese Umwandlung umfaßt zwei Stufen, nämlich Cyclisierung und β-Eliminierung von Halogenwasserstoff, aber es ist nicht klar, in welcher Reihenfolge diese beiden Stufen ablaufen, oder ob sie nicht sogar gemeinsam ablaufen. At least 2 moles of base are required in order to convert the compounds of the general formula (VIII) into the compounds of the general formula (IV), in which R represents alkoxy having 1 to 6 carbon atoms. This conversion involves two stages, namely cyclization and β- elimination of hydrogen halide, but it is not clear in which order these two stages proceed, or whether they do not even run together.
Wenn das Verfahren unter Verwendung von nur einem molaren Äquivalent der Base ausgeführt ist, dann werden drei verschiedene Produkte erhalten, wie sie im vorstehenden Anspruch 19 angegeben sind. Jede dieser Verbindungen ergibt bei Behandlung mit einem weiteren molaren Äquivalent einer Base eine erfindungsgemäße Verbindung.If the method using only one molar Equivalent of the base is executed, then three receive various products as described above Claim 19 are specified. Each of these connections results when treated with another molar equivalent a base a compound of the invention.
Die Verbindungen der allgemeinen Formel (VIII) des vorstehenden Anspruchs 17 können dadurch hergestellt werden, daß man eine Verbindung der FormelThe compounds of the general formula (VIII) of the above Claim 17 can be made that you have a compound of formula
worin Q für Alkoxy steht, mit einer Verbindung der Formelwherein Q is alkoxy with a compound of the formula
worin R¹, R², W′ und W′′ eine der oben angegebenen Bedeutungen besitzen, in Gegenwart eines radikalischen Initiators umsetzt. Hierbei kann es sich um einen physikalischen Inititator, z. B. Bestrahlung mit einer geeigneten Lichtquelle, z. B. einer UV-Lichtquelle, oder um einen herkömmlichen chemischen radikalischen Katalysator, z. B. Benzoylperoxid oder Azobisisobutyronitril, handeln. Das Verfahren kann bei Temperaturen im Bereich von 50 bis 150°C, vorzugsweise 80 bis 120°C, während Zeiten von 1 bis 20 h ausgeführt werden, und zwar gegebenenfalls in einem abgeschlossenen System und unter dem autogenen Druck der Reaktion.wherein R¹, R², W 'and W' 'one of the meanings given above own, in the presence of a radical initiator implements. This can be a physical Initiator, e.g. B. irradiation with a suitable Light source, e.g. B. a UV light source, or a conventional chemical radical catalyst, e.g. As benzoyl peroxide or azobisisobutyronitrile act. The process can be carried out at temperatures in the range of 50 to 150 ° C, preferably 80 to 120 ° C, during times of 1 up to 20 h, if necessary in a closed system and under the autogenous Pressure of reaction.
Die Erfindung wird durch die folgenden Beispiele näher erläutert. The invention is illustrated by the following examples explained.
Ein gerührtes Gemisch aus 235 g Hexafluoroaceton und 100 g 3-Methylbut-1-en wurde unter einem Druck
von 16,7 bar (17 at) während eines Zeitraums von 20 h auf 125°C erhitzt. Destillation des Produktgemischs unter vermindertem
Druck ergab 5-Hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoromethylhex-2-en als bewegliche farblose Flüssigkeit,
Kp. 43°C/20 mbar.
NMR (CCl₄) p.p.m. 1,77 (d, 6H); 2,58 bis 3,00 (m, 3H); 5,0 bis 5,4 (m, 1H).A stirred mixture of 235 g of hexafluoroacetone and 100 g of 3-methylbut-1-ene was heated to 125 ° C. under a pressure of 16.7 bar (17 at) over a period of 20 hours. Distillation of the product mixture under reduced pressure gave 5-hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoromethylhex-2-ene as a mobile colorless liquid, bp. 43 ° C./20 mbar.
NMR (CCl₄) ppm 1.77 (d, 6H); 2.58 to 3.00 (m, 3H); 5.0 to 5.4 (m, 1H).
Eine Lösung von 9,12 g Diazoessigsäure-äthylester in 400 ml Dichloromethan wurde tropfenweise während eines Zeitraums von 48 h in Gegenwart einer katalytischen Menge von wasserfreiem Kupfer(II)-sulfat bei 110 bis 120°C zu 18,9 g 5-Hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoromethylhex-2-en zugegeben.A solution of 9.12 g of ethyl diazoacetate in 400 ml of dichloromethane was added dropwise during 48 hours in the presence of a catalytic amount of anhydrous copper (II) sulfate at 110 to 120 ° C to 18.9 g of 5-hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoromethylhex-2-ene.
Das resultierende Gemisch wurde mit Wasser gewaschen, über wasserfreiem Magnesiumsulfat getrocknet und
destilliert, wobei mehrere Fraktionen innerhalb des Bereichs von 68 bis 90°C bei 20 m bar erhalten wurden.
NMR-, IR- und Massenspektralanalyse zeigte, das diese Fraktionen hauptsächlich aus den (±)-cis- und (±)-
trans-Isomeren von 3-(2-Hydroxy-3,3,3-trifluoro-2-trifluoromethylprop-1-yl)-2,2-dimethy-lcyclopropan-carbonsäure-
äthylester in verschiedenen Verhälnissen bestand.
NMR (CDCl₃) p.p.m. 1,04 bis 1,40 (m, 9H); 1,55 bis 2,43 (m, 4H) 4,00 bis 4,37 (m, 2H).The resulting mixture was washed with water, dried over anhydrous magnesium sulfate, and distilled to obtain several fractions within the range of 68 to 90 ° C at 20 m bar. NMR, IR and mass spectral analysis showed that these fractions mainly from the (±) -cis and (±) - trans isomers of 3- (2-hydroxy-3,3,3-trifluoro-2-trifluoromethylprop-1 -yl) -2,2-dimethyl-cyclopropane-carboxylic acid ethyl ester in various ratios.
NMR (CDCl₃) ppm 1.04 to 1.40 (m, 9H); 1.55 to 2.43 (m, 4H) 4.00 to 4.37 (m, 2H).
Ein Gemisch aus 4,62 g (±)-cis/trans-3-(2-Hydroxy-3,3,3-trifluoro-2-trifluoromethylprop-1-y-l)-2,2-dimethyl-
cyclopropan-carbonsäure-äthylester, 2,2 g Phosphoroxychlorid und 5,3 ml trockenem Pyridin wurde während
eines Zeitraums von 65 h auf 110°C erhitzt, worauf es in Eiswasser geschüttet und 5 h gerührt wurde. Das auf
diese Weise erhaltene Gemisch wurde mit Diäthyläther extrahiert, und die Extrakte wurden mit Wasser gewaschen
und über wasserfreiem Natriumsulfat getrocknet. Nach Entfernen des Äthers durch Abdampfen unter
vermindertem Druck wurde das zurückbleibende Öl unter vermindertem Druck destilliert. (±)-cis/trans-3-
(3,3,3-Trifluoro-2-trifluoromethylprop-1-en-1-yl)-2,2-dimethylcyclop-ropan-carbonsäure-äthylester wurde als farbloses
Öl, Kp. 60 bis 65°C/0 m bar, erhalten.
NMR (CDCl₃) p.p.m. 1,15 bis 1,39 (m, 9H); 1,75 bis 2,60 (m, 2H); 4,02 bis 4,34 (m, 2H); 6,36 und 7,36 (dd, 1H).A mixture of 4.62 g (±) -cis / trans-3- (2-hydroxy-3,3,3-trifluoro-2-trifluoromethylprop-1-yl) -2,2-dimethylcyclopropane-carboxylic acid ethyl ester , 2.2 g of phosphorus oxychloride and 5.3 ml of dry pyridine was heated to 110 ° C over a period of 65 h, after which it was poured into ice water and stirred for 5 h. The mixture thus obtained was extracted with diethyl ether, and the extracts were washed with water and dried over anhydrous sodium sulfate. After the ether was removed by evaporation under reduced pressure, the remaining oil was distilled under reduced pressure. (±) -cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid ethyl ester was used as a colorless oil, b.p. 60 to 65 ° C / 0 m bar, obtained.
NMR (CDCl₃) ppm 1.15 to 1.39 (m, 9H); 1.75 to 2.60 (m, 2H); 4.02 to 4.34 (m, 2H); 6.36 and 7.36 (dd, 1H).
Ein Gemisch aus 0,52 g (±)-cis/trans-3-(3,3,3-Trifluoro-2-trifluoromethylprop-1-en-1-yl)-2,-2-dimethylcyclopropan- carbonsäure-äthylester, 2,52 ml Eisessig, 3,36 ml 48%iger (G/V) Bromwasserstoffsäure und 1,12 ml Wasser wurde während eines Zeitraums von 10 h auf Rückflußtemperatur erhitzt. Nach dem Abkühlen wurde das Gemisch mit 50 ml Wasser verdünnt und mehrere Male mit Diäthyläther extrahiert. Die Extrakte wurden vereinigt, mit Wasser gewaschen, über wasserfreiem Natriumsulfat getrocknet und durch Eindampfen des Äthers unter vermindertem Druck konzentriert. Durch Spektroskopieanalyse wurde gezeigt, daß das zurückbleibende Öl im wesentlichen aus (±)-cis/trans-3-(3,3,3-Trifluoro-2-trifluoro-methylprop-1-en-1-yl)-2-,2-dimethyl- cyclopropan-carbonsäure bestand.A mixture of 0.52 g (±) -cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2, -2-dimethylcyclopropane carboxylic acid ethyl ester, 2.52 ml glacial acetic acid, 3.36 ml 48% (w / v) hydrobromic acid and 1.12 ml Water was heated to reflux temperature over a period of 10 hours. After cooling was down the mixture diluted with 50 ml of water and extracted several times with diethyl ether. The extracts were combined, washed with water, dried over anhydrous sodium sulfate and by evaporation of the Ether concentrated under reduced pressure. Spectroscopic analysis showed that the remaining Oil essentially from (±) -cis / trans-3- (3,3,3-trifluoro-2-trifluoro-methylprop-1-en-1-yl) -2-, 2-dimethyl- cyclopropane carboxylic acid existed.
Ein Gemisch aus 0,4 g (±)-cis/trans-3-(3,3,3-Trifluoro-2-trifluoromethylprop-1-en-1-yl)-2,-2-dimethylcyclopropan- carbonsäure und 5,0 ml Thionylchlorid wurde während eines Zeitraums von 2 h auf Rückflußtemperatur erhitzt, worauf das überschüssige Thionylchlorid durch Destillation unter vermindertem Druck entfernt wurde. Es blieb (±)-cis/trans-1-Chlorocarbonyl-3-(3,3,3-trifluoro-2-trifluoromethylp-rop-1-en-1-yl)-2,2-dimethylcyclopropan zurück. A mixture of 0.4 g (±) -cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2, -2-dimethylcyclopropane Carboxylic acid and 5.0 ml of thionyl chloride were refluxed over a 2 hour period heated, whereupon the excess thionyl chloride was removed by distillation under reduced pressure. There remained (±) -cis / trans-1-chlorocarbonyl-3- (3,3,3-trifluoro-2-trifluoromethylp-rop-1-en-1-yl) -2,2-dimethylcyclopropane back.
Ein Gemisch aus 7,0 g 3,3-Dimethylpent-4-ensäure-äthylester, 20,0 g 1,1,1-Trichloro-2,2,2-trifluoroäthan und 0,1 g Benzoylperoxid wurde in einem verschlossenen Glasrohr 5 h auf 100°C erhitzt. Das erhaltene Gemisch wurde sorgfältig destilliert, und 3,3-Dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptansäure-äthylester wurde als Fraktion mit einem Siedebereich von 112 bis 114°C/2,7 m bar gesammelt. Seine Identität wurde durch IR- und NMR-Spektroskopleanalyse bestätigt.A mixture of 7.0 g of 3,3-dimethylpent-4-enoic acid ethyl ester, 20.0 g of 1,1,1-trichloro-2,2,2-trifluoroethane and 0.1 g of benzoyl peroxide was heated in a sealed glass tube at 100 ° C for 5 h. The mixture obtained was carefully distilled and 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoic acid ethyl ester was used as Fraction with a boiling range of 112 to 114 ° C / 2.7 m bar collected. His identity was verified by IR and NMR spectroscopic analysis confirmed.
Der 3,3-Dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptansäureäthylester, der in Stufe A erhalten worden war, wurde in 30 ml trockenem Tetrahydrofuran aufgelöst, und die Lösung wurde tropfenweise zu einer Suspension von 2,75 g t-Butoxid, das in situ aus Natriumhydrid und t-Butylalkohol hergestellt worden war, in 120 ml trockenem Tetrahydrofuran bei 0°C zugegeben. Nach beendeter Zugabe wurde das Gemisch 2 h bei 0°C gerührt und dann mit äthanolischem Chlorwasserstoff angesäuert. Nach Verdünnung des Gemischs mit Diäthyläther wurde es mit Wasser gewaschen, über wasserfreiem Magnesiumsulfat getrocknet und durch Abdampfen der Lösungsmittel unter vermindertem Druck konzentriert. Das zurückbleibende gelbe Öl wurde sorgfältig unter vermindertem Druck destilliert, wobei (±)-cis/trans-3-(2-Chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethy-l- cyclopropan-carbonsäureäthylester, Kp. 70°C 0,67 mbar, erhalten wurde. NMR-Analyse zeigte, daß das Produkt aus einem Gemisch von ungefähr 60% des cis-Isomeren und ungefähr 40% des trans-Isomeren (am Cyclopropanring) bestand, wobei in jedem Fall ungefähr 90 bis 95% des Isomers, bei dem die Trifluoromethylgruppe sich in trans-Stellung zum Cyclopropanring an der Doppelbindung befindet (des Z-Isomere), und ungefähr 5 bis 10% des Isomers, bei dem sie sich in cis-Stellung befindet (das E-Isomer) erhalten werden.The 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoic acid ethyl ester obtained in step A was dissolved in 30 ml of dry tetrahydrofuran and the solution was added dropwise to a suspension 2.75 g of t-butoxide, prepared in situ from sodium hydride and t-butyl alcohol, in 120 ml of dry Tetrahydrofuran added at 0 ° C. After the addition had ended, the mixture was stirred at 0 ° C. for 2 h and then acidified with ethanolic hydrogen chloride. After dilution of the mixture with diethyl ether it was washed with water, dried over anhydrous magnesium sulfate and by evaporation of the Concentrated solvent under reduced pressure. The remaining yellow oil was carefully submerged distilled under reduced pressure, with (±) -cis / trans-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethy-l- cyclopropane-carboxylic acid ethyl ester, bp 70 ° C 0.67 mbar, was obtained. NMR analysis showed that the Product from a mixture of approximately 60% of the cis isomer and approximately 40% of the trans isomer (am Cyclopropane ring), in each case approximately 90 to 95% of the isomer in which the trifluoromethyl group is in the trans position to the cyclopropane ring on the double bond (of the Z isomer), and approximately 5 to 10% of the isomer in which it is in the cis position (the E isomer) is obtained.
Ein Gemisch aus 0,52 g (±)-cis/trans-3-(2-Chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethy-lcyclopropan- carbonsäure, 2,52 ml Eisessig, 3,36 ml 48%iger (G/V) Bromwasserstoffsäure und 1,12 ml Wasser wurde über einen Zeitraum von 10 h auf Rückflußtemperatur erhitzt. Nach Abkühlung wurde das Gemisch mit 50 ml Wasser verdünnt und mehrere Male mit Diäthyläther extrahiert. Die Extrakte wurden vereinigt, mit Wasser gewaschen, über wasserfreiem Natriumsulfat getrocknet und durch Abdampfen des Äthers unter vermindertem Druck konzentriert. Von dem zurückbleibenden Öl wurde durch Spektroskopieanalyse gezeigt, daß es hauptsächlich aus (±)-cis/trans-3-(2-Chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethy-lcyclopropan- carbonsäure bestand.A mixture of 0.52 g (±) -cis / trans-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl-cyclopropane carboxylic acid, 2.52 ml glacial acetic acid, 3.36 ml 48% (w / v) hydrobromic acid and 1.12 ml water was heated to reflux over a period of 10 hours. After cooling, the mixture was mixed with Diluted 50 ml of water and extracted several times with diethyl ether. The extracts were combined with Washed water, dried over anhydrous sodium sulfate and by evaporating the ether under concentrated under reduced pressure. The remaining oil was shown by spectroscopic analysis that it mainly consists of (±) -cis / trans-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl-cyclopropane carboxylic acid consisted.
Ein Gemisch aus 0,4 g (±)-cis/trans-3-(2-Chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethy-lcyclopropan- carbonsäure und 5,0 ml Thionylchlorid wurde 2 h auf Rückflußtemperatur erhitzt, worauf das überschüssige Thionylchlorid durch Destillation unter vermindertem Druck entfernt wurde. Es blieb (±)-cis/trans-1-Chlorocarbonyl- 3-(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropan zurück.A mixture of 0.4 g (±) -cis / trans-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl-cyclopropane carboxylic acid and 5.0 ml of thionyl chloride were heated at reflux temperature for 2 h, whereupon the excess Thionyl chloride was removed by distillation under reduced pressure. There remained (±) -cis / trans-1-chlorocarbonyl- 3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropane.
Claims (19)
-6. (±) -cis / trans-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropane-carboxylic acid.
-
- 7. (±) -cis / trans-3- (2-bromo-3,3,3-trifluoromethyl-prop-1-en-1-yl) -2,2-dimethylcyclopropane-carboxylic acid.
-
-8. (±) -cis / trans-3- (3,3,3-trifluoro-2-trifluoromethyl-prop-1-en-1-yl) -2,2-dimethylcyclopropane-carboxylic acid.
-
-9. (±) -cis / trans-3- (3-chloro-2,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropane-carboxylic acid.
-
- (a) eine Verbindung der allgemeinen Formel mit einem Niederalkylester von Diazoessigsäure behandelt, und
- (b) die erhaltene Verbindung der allgemeinen Formel mit einem chemischen Dehydratisierungsmittel dehydratisiert.
- (a) a compound of the general formula treated with a lower alkyl ester of diazoacetic acid, and
- (b) the compound of the general formula obtained dehydrated with a chemical dehydrating agent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB276377 | 1977-01-24 | ||
| GB1221077 | 1977-03-23 | ||
| GB3671477 | 1977-09-02 | ||
| GB3671577 | 1977-09-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2858248C2 true DE2858248C2 (en) | 1987-10-08 |
Family
ID=27447244
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2802962A Expired DE2802962C2 (en) | 1977-01-24 | 1978-01-24 | Cyclopropanecarboxylic acid ester derivatives and insecticidal compositions containing them |
| DE2858248A Expired DE2858248C2 (en) | 1977-01-24 | 1978-01-24 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2802962A Expired DE2802962C2 (en) | 1977-01-24 | 1978-01-24 | Cyclopropanecarboxylic acid ester derivatives and insecticidal compositions containing them |
Country Status (27)
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| JP (2) | JPS5395945A (en) |
| AR (1) | AR218651A1 (en) |
| BE (1) | BE863151A (en) |
| BR (1) | BR7800422A (en) |
| CA (1) | CA1246094A (en) |
| CH (1) | CH638171A5 (en) |
| DD (1) | DD138544A5 (en) |
| DE (2) | DE2802962C2 (en) |
| DK (1) | DK158784C (en) |
| EG (1) | EG13028A (en) |
| ES (3) | ES466281A1 (en) |
| FR (2) | FR2392964A1 (en) |
| GR (1) | GR65619B (en) |
| HU (1) | HU184685B (en) |
| IL (3) | IL53832A (en) |
| IT (1) | IT1092969B (en) |
| LU (1) | LU78930A1 (en) |
| NL (3) | NL189087C (en) |
| NZ (1) | NZ186256A (en) |
| PH (2) | PH13451A (en) |
| PL (1) | PL113130B1 (en) |
| PT (1) | PT67574B (en) |
| SE (3) | SE437263B (en) |
| TR (1) | TR20462A (en) |
| YU (1) | YU15078A (en) |
| ZM (1) | ZM1078A1 (en) |
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| US4183948A (en) * | 1977-01-24 | 1980-01-15 | Imperial Chemical Industries Limited | Halogenated esters |
| IN150399B (en) * | 1978-01-20 | 1982-09-25 | Fmc Corp | |
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| US4243677A (en) * | 1978-01-20 | 1981-01-06 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| US4235927A (en) * | 1978-01-20 | 1980-11-25 | Fmc Corporation | Insecticidal benzylfurylmethyl perhaloalkylvinylcyclopropanecarboxylates |
| US4328237A (en) * | 1978-02-28 | 1982-05-04 | Montedison S.P.A. | Pyrethroids |
| US4258202A (en) * | 1978-02-28 | 1981-03-24 | Montedison S.P.A. | Cyclopropanecarboxylic acids and esters |
| BG48921A3 (en) * | 1978-02-28 | 1991-06-14 | Montedison Spa | Method for destroying of insects |
| DE2819788A1 (en) * | 1978-05-05 | 1979-11-08 | Bayer Ag | Benzyl esters with fluorine-substituted ether and / or thioether groups and their use as insecticides |
| DE2831193A1 (en) * | 1978-07-15 | 1980-01-24 | Bayer Ag | FLUORALKENYL-SUBSTITUTED CYCLOPROPANCARBONIC ACID ESTERS AND THEIR USE AS INSECTICIDES |
| DE2842541A1 (en) * | 1978-09-29 | 1980-05-22 | Bayer Ag | FLUORALKENYL-SUBSTITUTED CYCLOPROPANCARBONIC ACID ESTERS AND THEIR USE AS INSECTICIDES |
| DE2965744D1 (en) * | 1978-10-27 | 1983-07-28 | Ici Plc | Process for separating optical isomers of substituted cyclopropane carboxylic acids; amine salts of substituted cyclopropane carboxylic acids; a substituted cyclopropane carboxylic acid |
| DE2964152D1 (en) * | 1978-10-31 | 1983-01-05 | Ici Plc | Process for the preparation of cyclopropane carboxylic acid esters |
| DE3060562D1 (en) * | 1979-02-14 | 1982-08-12 | Ici Plc | Esters of halogenated substituted cyclopropanoic acids, their preparation and use as insecticides |
| DE2916357A1 (en) * | 1979-04-23 | 1980-11-06 | Bayer Ag | METHOD FOR PRODUCING 3- (2-ARYL-VINYL) -2,2-DIMETHYL-CYCLOPROPAN-1-CARBONIC ACID ESTERS AND NEW INTERMEDIATE PRODUCTS THEREFOR |
| AU531541B2 (en) * | 1979-05-11 | 1983-08-25 | Pitman-Moore Australia Limited | Tickicidal composition |
| US4335252A (en) * | 1979-05-24 | 1982-06-15 | Fmc Corporation | Insecticidal pyrethroid enantiomer pair |
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| US4341796A (en) | 1979-06-25 | 1982-07-27 | Fmc Corporation | Control of acarids with biphenylmethyl perhaloalkylvinylcyclopropanecarboxylates |
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| EP0022608B1 (en) * | 1979-07-13 | 1983-07-06 | Imperial Chemical Industries Plc | Process for the preparation of cyclopropane carboxylic acid esters |
| DE2939913A1 (en) * | 1979-10-02 | 1981-04-30 | Bayer Ag, 5090 Leverkusen | 3- (2,3-DICHLOR-3,3-DIFLUOR-PROP-1-EN-1-YL) -2,2-DIMETHYL-CYCLOPROPANCARBONIC ACID FLUOR-BENZYL ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN PEST CONTROL |
| JPS5692830A (en) * | 1979-12-07 | 1981-07-27 | Ciba Geigy Ag | 22*2**2**dichloroo3**3**3**trifluoropropyl** and 22*2**2**3**trichloroo3**3** difluoropropyl**44chlorocyclobutanee11one and their manufacture |
| OA06786A (en) * | 1980-04-16 | 1982-12-31 | Roussel Uclaf | New derivatives of cyclopropane acid, their preparation, their application to the fight against parasites of plants and animals, the compositions containing them and the new intermediates obtained. |
| DE3019552A1 (en) * | 1980-05-22 | 1981-11-26 | Bayer Ag, 5090 Leverkusen | 3- (2-CHLORINE-3,3,4,4,4-PENTAFLUOR-1-BUTENYL) -2,2-DIMETHYL-CYCLOPROPANCARBONIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN PEST CONTROL |
| IT1150963B (en) * | 1980-07-29 | 1986-12-17 | Montedison Spa | PYRETHROIDS |
| EP0050776B1 (en) * | 1980-10-23 | 1983-11-16 | Bayer Ag | Process for the preparation of chloro-fluoroalkenyl-substituted cyclopropane-carboxylic-acid esters |
| US4368205A (en) * | 1980-10-31 | 1983-01-11 | Fmc Corporation | 4-Heterocyclic-substituted-2-indanyl alcohols and insecticidal ester derivatives |
| US4423255A (en) * | 1980-12-31 | 1983-12-27 | Fmc Corporation | (+)-4-Substituted-2-indanols |
| US4417078A (en) * | 1980-12-31 | 1983-11-22 | Fmc Corporation | Process for producing (+)-4-substituted-2-indanols |
| US4362744A (en) * | 1981-03-19 | 1982-12-07 | Fmc Corporation | Trans-3-substituted-1-indanol insecticidal ester derivatives |
| DE3225130A1 (en) * | 1981-07-10 | 1983-01-27 | National Research Development Corp., London | Benzyl alcohol derivatives, their preparation, and the pesticides using them |
| DE3127752A1 (en) * | 1981-07-14 | 1983-02-03 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING PERMETHRINSAEUREMENTHYLESTER |
| US4415748A (en) * | 1981-08-06 | 1983-11-15 | Fmc Corporation | Intermediates for insecticidal synthetic pyrethroids |
| AU550754B2 (en) * | 1981-11-27 | 1986-04-10 | Pitman-Moore Australia Limited | Levamisole and cyhalothrin compositions |
| NZ203574A (en) * | 1982-03-16 | 1986-04-11 | Wellcome Australia | Pour on compositions containing pyrethroids and thiazoles |
| ZA836964B (en) * | 1982-10-11 | 1984-05-30 | Ici Plc | Insecticidal product and preparation thereof |
| GB8308507D0 (en) * | 1983-03-28 | 1983-05-05 | Ici Plc | Insecticidal product |
| EP0106469B1 (en) * | 1982-10-11 | 1987-01-14 | Imperial Chemical Industries Plc | Insecticidal product and preparation thereof |
| LV5122A3 (en) * | 1982-10-11 | 1993-06-10 | Ici Plc | Substrate (1R, Cis) -3- (Z-Chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropionic acid and (R) -alpha-cyano-3- (Z- 2-Chloro-3,3,3-trifluoro-prop-1-en-1-yl) -2,2-dimethylcyclopropionic acid (S) -alpha-cyano-3-phenoxybenzyl ester isomer crystalline enantiomeric para |
| GB2128607A (en) * | 1982-10-18 | 1984-05-02 | Ici Plc | An enantiomeric pair of cyhalothrin isomers and process for preparation thereof |
| USH49H (en) | 1983-01-10 | 1986-04-01 | Fmc Corporation | Process for producing 3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylates |
| GB8418331D0 (en) * | 1984-07-18 | 1984-08-22 | Ici Plc | Insecticidal ester |
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| DE3900275A1 (en) * | 1989-01-07 | 1990-07-12 | Basf Ag | SUBSTITUTED CYCLOPROPANCARBONIC ACID PROPARGYL ESTERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING Pests |
| GB9311054D0 (en) * | 1993-05-28 | 1993-07-14 | Zeneca Ltd | Preparation of cyclopropane esters |
| FR2708930B1 (en) * | 1993-08-10 | 1995-09-08 | Roussel Uclaf | New esters derived from 2,2-dimethyl 3- (3,3,3-trifluoro-1-propenyl) cyclopropane carboxylic acid, their preparation process and their application as pesticides. |
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| DE19953775A1 (en) | 1999-11-09 | 2001-05-10 | Bayer Ag | Active ingredient combinations with insecticidal and acaricidal properties |
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| AR029677A1 (en) * | 2000-06-29 | 2003-07-10 | Bayer Ag | COMBINATIONS OF ACTIVE COMPOUNDS WITH INSECTICIDES AND ACARICIDES |
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| DE102004001271A1 (en) | 2004-01-08 | 2005-08-04 | Bayer Cropscience Ag | Drug combinations with insecticidal properties |
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| US20090281157A1 (en) * | 2006-07-11 | 2009-11-12 | Bayer Cropscience Ag | Active Ingredient Combinations With Insecticidal and Acaricidal Properties |
| DE102007007750A1 (en) * | 2006-08-17 | 2008-02-21 | Bayer Cropscience Ag | avermectin derivatives |
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| DE102007045953B4 (en) | 2007-09-26 | 2018-07-05 | Bayer Intellectual Property Gmbh | Drug combinations with insecticidal and acaricidal properties |
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| MX2011009918A (en) | 2009-03-25 | 2011-10-06 | Bayer Cropscience Ag | Active ingredient combinations having insecticidal and acaricidal properties. |
| DE102009028001A1 (en) | 2009-07-24 | 2011-01-27 | Bayer Cropscience Ag | Use of an active agent combination (comprising a 3-phenyl-1-aza-spiro(4.5)dec-3-en-2-one compound, and an agent e.g. alanycarb, aldicarb, acephate, camphechlor or chlordane) for combating animal pests e.g. insects, acarids and helminths |
| EP2382865A1 (en) | 2010-04-28 | 2011-11-02 | Bayer CropScience AG | Synergistic active agent compounds |
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| JPS515450B1 (en) * | 1971-06-29 | 1976-02-20 | ||
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1978
- 1978-01-16 US US05/869,615 patent/US4183948A/en not_active Expired - Lifetime
- 1978-01-17 IL IL53832A patent/IL53832A/en unknown
- 1978-01-18 HU HU78IE821A patent/HU184685B/en unknown
- 1978-01-18 NZ NZ186256A patent/NZ186256A/en unknown
- 1978-01-19 CA CA000295309A patent/CA1246094A/en not_active Expired
- 1978-01-20 BE BE184513A patent/BE863151A/en not_active IP Right Cessation
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